Anthracene dye and process of making same.



UNTTED STATES PATENT. @FFICE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR' TO BADISCHE ANILIN & SODAFABRIK, OF LUDWIGSHAFEN, GERMANY, A CORPORATION OF GERMANY.

ANTHRACENE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 707,374, dated August19, 1902.

Application filed July 2, 1901. Serial No. 661898 (No specimens.)

To all whom it may concern.-

Be it known that I, OSCAR BALLY, doctor of philosophy and chemist, acitizen of the Swiss Republic, residing at Mannheim, in the GrandDuchy'of Baden, Germany, have in vented new and useful Improvements inColoring-Matter of the Anthracene Series and Process of Producing Same,of which the following is a specification.

It is known that by the action of primary aromatic amins on certainnitro-anthraquinone bodies-such as dinitro -anthraquinone,nitro-anthraquinone sulfo-acid, hydroxy-nitroanthraquinone, tetra nitroanthrach rysone, and the like-products are formed which, if

not directly suitable for use as dyestuffs, can be converted intodyestuffs by simple meansfor example, by sulfonatipn. In these casesaromatic amins-that is, basic bodiesare condensed withnitro-anthraquinones, and it is believed that a substitution ofalphyl-amido group for nitro group takes place thereby.

Ihave discovered that the above-mentioned class of nitro-anthraquinonebodiesthat is to say, such nitro-anthraquinones and derivatives ofnitro-an'thraquinones as, on condensation with primary aromatic amins,yield coloring-matters or bodies easily convertible intocoloring-matters, as hereinbefore mentionedcan be condensed with thesulfo-acids of primary aromatic amins, compounds which, in most cases,are not of a basic character. The reaction is best carried out in thepresence of water, the sulfo-acid dissolved 5 or suspended in waterbeing heated with the desired nitro-anthraquinone body either at thetemperature of the water-bath or at a higher temperature and underpressure, as the circumstances may require.

The following examples will serve to further illustrate the nature ofmyinvention and a manner of carrying the same into practical effect; butthe invention is not confined to the examples. The parts are by weight.

Example 1Procluction of coloring-matter from 1.8-d'nilr0-anthraquin0neand sodium sulfam'lale.-Mix together in an enameled autoclave one (1)part of 1.8-dinitro-anthraquinone, one 1) part of sodium sulfanilate,(containing water of crystallization and five (5) parts of water andheat the mixture for four (4) hours at a temperature of two hundred(200) degrees centigrade. The pressure rises to about twenty-five (25)atmospheres. When cold, dilute the red reaction product with Water,filter ofi any unchanged dinitroanthra-quinone present,-and precipitatethe coloring-matter from the filtrate by means of common salt. In placeof 1.8-dinitro-anthraquinone another isomeric anthraquinone can beused,or the crude mixture of nitr0-anthraquinones obtained by nitratinganthra-' quinone may be employed in this example.

Example 2Produclton of coloring-mailer from m0noudro-anthraqu'luonesulfo-acid and sodium sulfanilate.Heat together in an autoclave one (1)part of crude mononitroanthraquinone monosulfoacid,(obtainablebynitratingan-thraquinone monosulfo-acid,) one (1) part of sodiumsulfanilate, (containing water of crystallization,) and twenty-five (25)parts of water for four (4) hours at a temperature of two hundred (200)degrees centigrade.

Allow to cool and precipitate the red dyestufl? formed by means ofcommon salt.

Example 3P'r0ducliou of coloring-mailer f rom mououilro-anlhraquinouesulfa-acid and sodium metauilate.--Heat together in an autoclave one (1)part of crude mononitroanthraquinone' monosulfo-acid, one (1) part of apaste of sodium metanilate, (containing eighty-five per cent. of sodiummetanilate,)' and five (5) parts of water for five (5) hours at atemperature of two hundred (200) degrees centigrade. Allow to cool andprecipitate, by means of potassium chlorid, the coloring-matter from thebrown solution obtained.

Example 4Pr0ductiou of coloring-mailer from d'm'ltro-aulhrachrysoned'lsulfo-acz'd and 0 sodium sulfanilate.Heat together on the boilingWater-bath one (1) part of dinitroanthrachrysone disulfo-acid, three (3)parts of sodium sulfanilate, (containing Water of crystallization,) andtwenty (20) parts of 5 Water. The solution is at first brown, but

gradually becomes violet, and finally blue. Salt out thecoloring-matter, press, and dry.

In the preceding examples sodium metanilate can be substituted forsodium sulfani- 10o late, and vice versa. Other amido sulfo-acids of thebenzene series and the naphthalene series can also be employed.

My new coloring-matter thus obtained dyes unmordanted Wool and woolmordanted with metallic salts.

mordanted Wool can be subsequently treated with metallic salts and theshades thereby modified, if desired.

Some of the properties of the new coloringmatter obtainable according tomy invention The dyeings produced on una are set forth in the followingtable:

\ Sulfuric V z -1 9H Dyes Condensation prod- (Jaustlc- Sodium uar-Glacial Sulfuric V tl x VA Al h l, 1 I I I withaddichrome-inor- LlLli11o1n-- soda lye. bonate. 1 acetic acid. aud Jo t i q n o f duntedwoul.

[ 5 bone acid.

1.8 dinitro anthra- Easily sol- Color not changed Soluble cherry-red Y el l 0 W O n lo n g Violeta'ed.

qunione sulfa uble; redbrown. standing nihc acid. violet. blue.

Crude dinitro-antlo, do do Olive On long Dull violetthraquinone 5111-stan (l i n g red. fanllic acid. (lull violet.

Crude nitro-anthra Easily sol- Solution somewhat more Hardly sol Fairlyeasily Olive O 11 lo 11g RLiI.

quuione monosuluble: fucllviolet. uhie. soluble; stand in gtirfluid-lsulfanilic sine red. yellow-redv claret-rod. acid.

Crude nitro-anthra- Easily sol- Dull violet Fairly soluble: orange BrownOn 10 n i: It e d d i s11 quinone monosul ublo: 1'6(lstandi ug brown.toaeid+metanilio brown. v I 0 l 0 i3 acld. brown.

Dillitl'o-anthrachry- Easily sol- Somewhat I Violet llll Hardly solubleY c l l 0 A t O 11 C 6 Green-blue. sone disulfo acid uble: 'vioredder.brown. green-blue.

+ sulfanilic acid. let-blue.

stance; which are soluble in Water with a reddish-brown to violet-bluecolor; soluble in glacial acetic acid with a reddish to orange color;soluble in concentrated sulfuric acid with a yellow-brown to violetcolor.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing Witnesses.

OSCAR BALLY.

\Vitnesses:

JACOB ADRIAN,

JOHN L. HEINKE.

